CN110637833A - Indoor antibacterial nano catalytic material and preparation method thereof - Google Patents
Indoor antibacterial nano catalytic material and preparation method thereof Download PDFInfo
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- CN110637833A CN110637833A CN201910725664.7A CN201910725664A CN110637833A CN 110637833 A CN110637833 A CN 110637833A CN 201910725664 A CN201910725664 A CN 201910725664A CN 110637833 A CN110637833 A CN 110637833A
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- maleic anhydride
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 126
- 239000000463 material Substances 0.000 title claims abstract description 77
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 140
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 239000002245 particle Substances 0.000 claims abstract description 73
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 27
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 25
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001841 potassium permanganate Drugs 0.000 description 21
- 230000001954 sterilising effect Effects 0.000 description 17
- 238000004659 sterilization and disinfection Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 231100000597 Sick building syndrome Toxicity 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 and simultaneously Chemical compound 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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Abstract
The invention relates to an indoor antibacterial nano catalytic material and a preparation method thereof, wherein in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, an ultrasonic nano device is adopted to treat a reaction system, guanidine hydrochloride and maleic anhydride are added into the reaction system when the reaction is carried out for 3-6 min, and the temperature is rapidly reduced to above 9 ℃/min after the reaction is carried out for 10-15 minPreparing an indoor antibacterial nano catalytic material at the temperature of below-10 ℃; the finally prepared indoor antibacterial nano catalytic material is porous particles loaded with antibacterial functional maleic anhydride; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m2The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm. The preparation method is simple and feasible, and the indoor antibacterial nano catalytic material prepared by the method has excellent antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and relates to an indoor antibacterial nano catalytic material and a preparation method thereof.
Background
In recent years, with the improvement of living standard and the enhancement of health consciousness of people, people pay more attention to indoor air quality of buildings. According to the research of the united states Environmental Protection Agency (EPA), it is shown that indoor air of homes and office buildings is more seriously polluted than air of industrialized cities. Meanwhile, people stay indoors for 90% of the time, so that the pollution of indoor air is more harmful to the health of human bodies than the pollution of outdoor air. Deterioration of indoor air quality directly leads to sick building syndrome and building morbidity. The microorganisms such as bacteria and fungi propagate indoors to pollute the air, which is an important public environmental sanitation problem at present. The case that the indoor air microbial pollution causes human health influence happens occasionally, and even the case that the indoor air microbial pollution causes life threatening influence is not rare. Indoor sterilization becomes an important concern.
There are generally three ways to sterilize indoors: sterilizing with a sterilizing lamp, sterilizing with a liquid bactericide, and sterilizing with ozone. Wherein, the disinfection lamp has the defects of limited action distance, incapability of sterilizing dead corners and the like; the liquid bactericide mainly comprises chemical components which are possibly harmful to human bodies, and when the liquid components are volatilized into the air, the liquid bactericide is easy to absorb into the human bodies to cause potential harm; ozone is a strong oxidant, which is harmful to human body and is not approved for final use.
Therefore, the research of a new material for indoor sterilization is of great significance.
Disclosure of Invention
The invention aims to solve the problem of poor sterilization effect of indoor sterilization materials in the prior art, and provides an indoor antibacterial nano catalytic material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of an indoor antibacterial nano catalytic material comprises the steps of treating a reaction system by using an ultrasonic nano device in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, adding guanidine hydrochloride and maleic anhydride into the reaction system when the reaction is carried out for 3-6 min, and rapidly cooling to the temperature below-10 ℃ at the speed of more than 9 ℃/min after the reaction is carried out for 10-15 min to obtain the indoor antibacterial nano catalytic material.
In the invention, guanidine hydrochloride and maleic anhydride are added in the synthesis process of manganese dioxide, and react to generate the antibacterial functional maleic anhydride, and the antibacterial functional maleic anhydride is uniformly loaded on the surface of the manganese dioxide through hydrogen bonds because the guanidine hydrochloride and the maleic anhydride are added at a specific stage (reacting for 3-6 min), and the manganese dioxide has a sterilization effect, and the sterilization mechanism is as follows: manganese dioxide has strong oxidizing property, can oxidize and damage cells, and gradually leads to cell inactivation, and the antibacterial functional maleic anhydride also has a sterilization effect, after the antibacterial functional maleic anhydride is loaded on the surface of the manganese dioxide, the antibacterial functional maleic anhydride enhances the sterilization effect of the manganese dioxide, and simultaneously, the manganese dioxide can oxidize sulfydryl in bacterial metabolic enzyme by virtue of the strong oxidizing property of the manganese dioxide per se so as to inactivate the enzyme, so that bacteria die due to incapability of metabolism, cations of organic guanidine in the antibacterial functional maleic anhydride can generate electrostatic adsorption with anions on the surfaces of the bacterial cells, and the surface structure of the bacteria is damaged, so that the high-efficiency sterilization can be realized, a certain synergistic effect can be realized, and the sterilization effect of the material is further enhanced;
in addition, compared with the prior art, the method for synthesizing manganese dioxide of the present invention has the following differences:
1) the reaction system is treated by the ultrasonic nanocrystallization device, so that the particle size of the nano manganese dioxide particles is smaller than that of manganese dioxide nano particles prepared by the reaction system without the ultrasonic nanocrystallization device, the specific surface area of the manganese dioxide nano particles is favorably improved, the contact surface of manganese dioxide and bacteria can be enhanced after the specific surface area is improved, the sulfydryl in manganese dioxide oxidizing bacteria metabolic enzyme is further enhanced, the enzyme is inactivated, and the bacteria can die quickly due to the incapability of metabolism;
2) after reacting for a period of time, rapidly cooling to below-10 ℃, the temperature is slowly reduced after the reaction is finished in the existing reaction, the rapid cooling is favorable for rapidly terminating the reaction, and preventing the generated manganese dioxide particles from further growing, because the manganese dioxide powder can grow gradually along with the reaction in the reaction process, the temperature is a necessary condition for promoting the reaction, the reaction can be inhibited by instantly reducing the temperature, the further growth of the powder is prevented, a large amount of water molecules are remained in the formed manganese dioxide powder after the rapid cooling, a porous structure can be formed after the prepared manganese dioxide is put into a liquid water evaporation under a normal temperature environment, and the specific surface area of the manganese dioxide is improved; if the temperature does not reach below-10 ℃, the reaction still proceeds slowly, resulting in a larger final particle size.
As a preferable scheme:
according to the preparation method of the indoor antibacterial nano catalytic material, before the reaction starts, the reaction system consists of potassium permanganate, manganese salt and water.
According to the preparation method of the indoor antibacterial nano catalytic material, before the reaction starts, the molar ratio of potassium permanganate, manganese salt and water in a reaction system is 1: 2-4: 6-7, the range is the most suitable molar ratio, and the reaction is insufficient when the ratio is too large or too small; the molar ratio of guanidine hydrochloride to maleic anhydride is 2-4: 1, and guanidine hydrochloride is used for carrying out antibacterial functional treatment on maleic anhydride, so that the content of guanidine hydrochloride is higher, the mass addition amount of maleic anhydride is 1.2-2 times of that of potassium permanganate, the effect of manganese dioxide is weakened when the mass addition amount of maleic anhydride is too large, and the comprehensive antibacterial performance is deteriorated when the mass addition amount of maleic anhydride is too small.
In the preparation method of the indoor antibacterial nano catalytic material, the manganese salt is more than one of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.
The preparation method of the indoor antibacterial nano catalytic material comprises the following specific steps: firstly, heating a reaction system consisting of potassium permanganate, manganese salt and water to 80-100 ℃ for reaction for A min, treating the reaction system with an ultrasonic nano device, then adding guanidine hydrochloride and maleic anhydride into the reaction system, continuing to react for B min, treating the reaction system with the ultrasonic nano device, and finally rapidly cooling to-10-30 ℃ at the speed of 9-20 ℃/min, and treating the reaction system with the ultrasonic nano device; a is 3-6, and the sum of A and B is 10-15.
According to the preparation method of the indoor antibacterial nano catalytic material, the working frequency range of the ultrasonic nano device is 20-25 KHz, the ultrasonic wave is in the range, the ultrasonic wave has obvious influence on the synthesis of the material, the particles can be uniformly distributed, the size reaches the nanometer level, the ultrasonic crushing effect is optimal at the frequency, and the crushing effect can be reduced when the frequency is higher or lower than the frequency.
The invention also provides an indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material, which is porous particles loaded with antibacterial functional maleic anhydride; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m2The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm.
As a preferable scheme:
the indoor antibacterial nano catalytic material has the average particle size of the porous particles of 10-30 nm and the specific surface area of 300-600 g/m2The porosity is 40-70%, and the pore diameter of the porous material is 3-5 nm.
According to the indoor antibacterial nano catalytic material, the antibacterial rate of the indoor antibacterial nano catalytic material is 99-99.999%.
Has the advantages that:
(1) according to the preparation method of the indoor antibacterial nano catalytic material, guanidine hydrochloride and maleic anhydride are added in the process of synthesizing manganese dioxide, and antibacterial functional maleic anhydride generated by the reaction of the guanidine hydrochloride and the maleic anhydride is uniformly loaded on the surface of the manganese dioxide through hydrogen bonds, so that the antibacterial performance of the manganese dioxide is greatly improved;
(2) the indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material has excellent antibacterial performance and better application prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese sulfate and water in a molar ratio of 1:2:7 to 80 ℃ for reaction for 6min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 20 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.2 times of that of potassium permanganate) into a reaction system in a molar ratio of 2:1, and continuing to react for 7min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 20 KHz;
(3) rapidly cooling to-10 deg.C at a rate of 9 deg.C/min, and treating with ultrasonic nano device with working frequency of 20 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size is 22nm, and the specific surface area is 456g/m2The porosity is 58%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.992%.
Comparative example 1
The basic steps of the preparation method of the indoor antibacterial nano catalytic material are the same as those of the example 1, except that the reaction system is not treated by an ultrasonic nano device in the steps (1), (2) and (3), and the finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 80nm, and the specific surface area of the porous manganese dioxide particles is 12g/m2The porosity is 10%, the pore diameter of the porous material is 5-6 nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 95%;
as can be seen from comparison between example 1 and comparative example 1, the nano manganese dioxide particles prepared in example 1 have smaller particle size, higher specific surface area and better sterilization effect, because the reaction system is treated by the ultrasonic nano-device in the whole reaction process in example 1, so that the particle size of the nano manganese dioxide particles is smaller than that of the manganese dioxide nanoparticles prepared without the ultrasonic nano-device, which is beneficial to improving the specific surface area and oxidation capability of the manganese dioxide nanoparticles.
Comparative example 2
The basic steps of the preparation method of the indoor antibacterial nano catalytic material are the same as those of the embodiment 1, except that the temperature reduction rate in the step (3) is 5 ℃/min, and the finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the particles is 40nm, and the specific surface area of the particles is 30g/m2The porosity is 24%, the pore diameter of the porous material is 5-6 nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 97%;
as can be seen from comparison between example 1 and comparative example 2, the manganese dioxide particles produced in example 1 have smaller particle size, better sterilization effect and higher porosity, because rapid temperature reduction facilitates rapid termination of the reaction and prevents further enlargement of the produced manganese dioxide particles.
Comparative example 3
The basic steps of the preparation method of the indoor antibacterial nano catalytic material are the same as those of the embodiment 1, except that the temperature is rapidly reduced to the room temperature in the step (3), and the finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 78nm, and the specific surface area of the porous manganese dioxide particles is 14g/m2The porosity is 13%, the pore diameter of the porous material is 5-6 nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 95%;
as can be seen from comparison of example 1 with comparative example 3, the manganese dioxide particles produced in example 1 have a smaller particle size, a higher antibacterial activity and a higher porosity, because lowering to room temperature does not prevent the reaction from proceeding.
Comparative example 4
A method for preparing indoor antibacterial nano catalytic material, which has the same basic steps as the embodiment 1,the difference is that the reaction in the step (1) is carried out for 13min, the step (2) is not carried out, the reaction is directly carried out in the step (3), and finally the prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles, the average particle size of the particles is 23nm, and the specific surface area of the particles is 410g/m2The porosity is 50%, the porous aperture is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 97%;
comparing example 1 with comparative example 4, it can be seen that the antibacterial effect of the antibacterial nanocatalysis material in example 1 is better, because manganese dioxide has strong oxidizing property, and can oxidize and destroy cell structures, which gradually leads to cell inactivation, the antibacterial functionalized maleic anhydride also has bactericidal effect, after the antibacterial functionalized maleic anhydride generated by the reaction of guanidine hydrochloride and maleic anhydride is loaded on the surface of manganese dioxide, the antibacterial functionalized maleic anhydride enhances the bactericidal effect of manganese dioxide, and simultaneously, manganese dioxide and the antibacterial functionalized maleic anhydride can also play a certain synergistic effect, further enhancing the bactericidal effect of the material.
Example 2
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese chloride and water in a molar ratio of 1:4:6 to 86 ℃ for reaction for 3min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.5 times of that of potassium permanganate) into a reaction system at a molar ratio of 3:1, and continuing to react for 7min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(3) rapidly cooling to-12 deg.C at a rate of 15 deg.C/min, and treating with ultrasonic nano device with working frequency of 25 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 20nm, and the specific surface area of the porous manganese dioxide particles is 529g/m2The porosity is 62%, the porous aperture is 3-5nm, and the indoor antibacterial nano-catalyst materialThe antibacterial rate of the material is 99.93%.
Example 3
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese oxalate and water in a molar ratio of 1:2:6 to 88 ℃ for reaction for 5min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 22 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.7 times of that of potassium permanganate) into a reaction system at a molar ratio of 3:1, and continuing to react for 7min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 22 KHz;
(3) rapidly cooling to-16 deg.C at a speed of 11 deg.C/min, and treating with ultrasonic nano device with working frequency of 22 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 14nm, and the specific surface area of the porous manganese dioxide particles is 548g/m2The porosity is 65%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.97%.
Example 4
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese carbonate and water in a molar ratio of 1:3:6 to 90 ℃ for reaction for 6min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.9 times of that of potassium permanganate) into a reaction system at a molar ratio of 4:1, and continuing to react for 9min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(3) rapidly cooling to-18 deg.C at a rate of 18 deg.C/min, and treating with ultrasonic nano device with working frequency of 25 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 12nm, and the specific surface area of the porous manganese dioxide particles is 565g/m2The porosity is 67%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.999%.
Example 5
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese acetate and water in a molar ratio of 1:3:7 to 100 ℃ for reaction for 4min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.4 times of that of potassium permanganate) into a reaction system at a molar ratio of 4:1, and continuing to react for 8min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(3) rapidly cooling to-20 deg.C at a rate of 20 deg.C/min, and treating with ultrasonic nano device with working frequency of 25 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 10nm, and the specific surface area of the porous manganese dioxide particles is 600g/m2The porosity is 70%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.8%.
Example 6
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of a mixture (mass ratio is 1:1) of potassium permanganate, manganese sulfate and manganese chloride with a molar ratio of 1:4:6 and water to 80 ℃ for reaction for 5min, and treating by an ultrasonic nano device with the working frequency of 20 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.3 times of that of potassium permanganate) into a reaction system at a molar ratio of 3:1, and continuing to react for 6min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 20 KHz;
(3) rapidly cooling to-10 deg.C at a rate of 9 deg.C/min, and treating with ultrasonic nano device with working frequency of 20 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 30nm, and the specific surface area of the porous manganese dioxide particles is 300g/m2The porosity is 40%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.91%.
Example 7
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, a mixture (manganese sulfate, manganese carbonate and manganese oxalate in a mass ratio of 1:2: 1) and water in a molar ratio of 1:4:7 to 95 ℃ for reaction for 4min, and treating by an ultrasonic nano device with the working frequency of 20 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 1.6 times of that of potassium permanganate) into a reaction system at a molar ratio of 3:1, and continuing to react for 10min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 20 KHz;
(3) rapidly cooling to-26 deg.C at a speed of 12 deg.C/min, and treating with ultrasonic nano device with working frequency of 20 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 18nm, and the specific surface area of the porous manganese dioxide particles is 511g/m2The porosity is 53%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.90%.
Example 8
A preparation method of indoor antibacterial nano catalytic material comprises the following basic steps:
(1) heating a reaction system of potassium permanganate, manganese sulfate and water in a molar ratio of 1:2:7 to 90 ℃ for reaction for 6min, and treating with an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(2) adding guanidine hydrochloride and maleic anhydride (wherein the mass addition amount of the maleic anhydride is 2 times of that of potassium permanganate) into a reaction system in a molar ratio of 2:1, and continuing to react for 6min with treatment of an ultrasonic nano device, wherein the working frequency of the ultrasonic nano device is 25 KHz;
(3) rapidly cooling to-30 deg.C at a rate of 20 deg.C/min, and treating with ultrasonic nano device with working frequency of 25 KHz.
The finally prepared indoor antibacterial nano catalytic material is porous manganese dioxide particles loaded with antibacterial functional maleic anhydride, the average particle size of the porous manganese dioxide particles is 12nm, and the specific surface area of the porous manganese dioxide particles is 575g/m2The porosity is 68%, the pore diameter of the porous material is 3-5nm, and the antibacterial rate of the indoor antibacterial nano catalytic material is 99.999%.
Claims (9)
1. A preparation method of an indoor antibacterial nano catalytic material is characterized by comprising the following steps: in the whole process of synthesizing manganese dioxide by taking potassium permanganate and manganese salt as raw materials, an ultrasonic nano device is adopted to treat a reaction system, guanidine hydrochloride and maleic anhydride are added into the reaction system when the reaction is carried out for 3-6 min, and the indoor antibacterial nano catalytic material is prepared by rapidly cooling to below-10 ℃ at a speed of more than 9 ℃/min after the reaction is carried out for 10-15 min.
2. The method for preparing indoor antibacterial nanocatalysis material as claimed in claim 1, wherein before the reaction, the reaction system consists of potassium permanganate, manganese salt and water.
3. The preparation method of the indoor antibacterial nano catalytic material according to claim 2, characterized in that before the reaction starts, the molar ratio of potassium permanganate, manganese salt and water in the reaction system is 1: 2-4: 6-7; the molar ratio of guanidine hydrochloride to maleic anhydride is 2-4: 1, and the mass addition amount of the maleic anhydride is 1.2-2 times of that of the potassium permanganate.
4. The method as claimed in claim 2, wherein the manganese salt is one or more of manganese sulfate, manganese chloride, manganese oxalate, manganese carbonate and manganese acetate.
5. The preparation method of the indoor antibacterial nano catalytic material according to claim 2, characterized by comprising the following specific steps: firstly, heating a reaction system consisting of potassium permanganate, manganese salt and water to 80-100 ℃ for reaction for A min, treating the reaction system with an ultrasonic nano device, then adding guanidine hydrochloride and maleic anhydride into the reaction system, continuing to react for B min, treating the reaction system with the ultrasonic nano device, and finally rapidly cooling to-10-30 ℃ at the speed of 9-20 ℃/min, and treating the reaction system with the ultrasonic nano device; a is 3-6, and the sum of A and B is 10-15.
6. The preparation method of the indoor antibacterial nano catalytic material as claimed in claim 5, wherein the working frequency range of the ultrasonic nano device is 20-25 KHz.
7. The indoor antibacterial nano catalytic material prepared by the preparation method of the indoor antibacterial nano catalytic material as claimed in any one of claims 1 to 6, is characterized in that: the antibacterial functional maleic anhydride-loaded porous particles are prepared by the following steps; the antibacterial functional maleic anhydride is generated by the reaction of guanidine hydrochloride and maleic anhydride; the porous particles are made of manganese dioxide, the average particle size is less than or equal to 30nm, and the specific surface area is more than or equal to 300g/m2The porosity is more than or equal to 40 percent, and the pore diameter of the porous material is less than or equal to 5 nm.
8. The indoor antibacterial nanocatalysis material as claimed in claim 7, wherein the porous particles have an average particle size of 10-30 nm and a specific surface area of 300-600 g/m2The porosity is 40-70%, and the pore diameter of the porous material is 3-5 nm.
9. The indoor antibacterial nanocatalysis material of claim 7 or 8, wherein the antibacterial rate of the indoor antibacterial nanocatalysis material is 99-99.999%.
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